p-Type Doping of GaN Nanowires Characterized by Photoelectrochemical Measurements.

GaN nanowires (NWs) doped with Mg as a p-type impurity were grown on Si(111) substrates by plasma-assisted molecular beam epitaxy. In a systematic series of experiments, the amount of Mg supplied during NW growth was varied. The incorporation of Mg into the NWs was confirmed by the observation of donor-acceptor pairs and acceptor-bound excitons in low-temperature photoluminescence spectroscopy. Quantitative information about the Mg concentrations was deduced from Raman scattering by local vibrational modes related to Mg. In order to study the type and density of charge carriers present in the NWs, we employed two photoelectrochemical techniques, open-circuit potential and Mott-Schottky measurements. Both methods showed the expected transition from n-type to p-type conductivity with increasing Mg doping level, and the latter characterization technique allowed us to quantify the charge carrier concentration. Beyond the quantitative information obtained for Mg doping of GaN NWs, our systematic and comprehensive investigation demonstrates the benefit of photoelectrochemical methods for the analysis of doping in semiconductor NWs in general.

Metal-Exchange Catalysis in the Growth of Sesquioxides: Towards Heterostructures of Transparent Oxide Semiconductors.

We observe that the growth rate of Ga_{2}O_{3} in plasma-assisted molecular beam epitaxy can be drastically enhanced by an additional In supply. This enhancement is shown to result from a catalytic effect, namely, the rapid formation of In_{2}O_{3}, immediately followed by a transformation of In_{2}O_{3} to Ga_{2}O_{3} due to an In-Ga interatomic exchange. We derive a simple model that quantitatively describes this process as well as its consequences on the formation rate of Ga_{2}O_{3}. Moreover, we demonstrate that the catalytic action of In_{2}O_{3} allows the synthesis of the metastable hexagonal phase of Ga_{2}O_{3}. Since the Ga_{2}O_{3}(0001)/In_{2}O_{3}(111) interface is closely lattice matched, this novel growth mode opens a new path for the fabrication of sesquioxide heterostructures.

Light coupling between vertical III-As nanowires and planar Si photonic waveguides for the monolithic integration of active optoelectronic devices on a Si platform.

We present a new concept for the optical interfacing between vertical III-As nanowires and planar Si waveguides. The nanowires are arranged in a two-dimensional array which forms a grating structure on top of the waveguide. This grating enables light coupling in both directions between the components made from the two different material classes. Numerical simulations show that this concept permits a light extraction efficiency from the waveguide larger than 45% and a light insertion efficiency larger than 35%. This new approach would allow the monolithic integration of nanowire-based active optoelectronics devices, like photodetectors and light sources, on the Si photonics platform.

Computing Equilibrium Shapes of Wurtzite Crystals: The Example of GaN.

Crystal morphologies are important for the design and functionality of devices based on low-dimensional nanomaterials. The equilibrium crystal shape (ECS) is a key quantity in this context. It is determined by surface energies, which are hard to access experimentally but can generally be well predicted by first-principles methods. Unfortunately, this is not necessarily so for polar and semipolar surfaces of wurtzite crystals. By extending the concept of Wulff construction, we demonstrate that ECSs can nevertheless be obtained for this class of materials. For the example of GaN, we identify different crystal shapes depending on the chemical potential, shedding light on experimentally observed GaN nanostructures.

Surface reconstruction-induced coincidence lattice formation between two-dimensionally bonded materials and a three-dimensionally bonded substrate.

Sb2Te3 films are used for studying the epitaxial registry between two-dimensionally bonded (2D) materials and three-dimensional bonded (3D) substrates. In contrast to the growth of 3D materials, it is found that the formation of coincidence lattices between Sb2Te3 and Si(111) depends on the geometry and dangling bonds of the reconstructed substrate surface. Furthermore, we show that the epitaxial registry can be influenced by controlling the Si(111) surface reconstruction and confirm the results for ultrathin films.

Coaxial multishell (In,Ga)As/GaAs nanowires for near-infrared emission on Si substrates.

Efficient infrared light emitters integrated on the mature Si technology platform could lead to on-chip optical interconnects as deemed necessary for future generations of ultrafast processors as well as to nanoanalytical functionality. Toward this goal, we demonstrate the use of GaAs-based nanowires as building blocks for the emission of light with micrometer wavelength that are monolithically integrated on Si substrates. Free-standing (In,Ga)As/GaAs coaxial multishell nanowires were grown catalyst-free on Si(111) by molecular beam epitaxy. The emission properties of single radial quantum wells were studied by cathodoluminescence spectroscopy and correlated with the growth kinetics. Controlling the surface diffusivity of In adatoms along the NW side-walls, we improved the spatial homogeneity of the chemical composition along the nanowire axis and thus obtained a narrow emission spectrum. Finally, we fabricated a light-emitting diode consisting of approximately 10(5) nanowires contacted in parallel through the Si substrate. Room-temperature electroluminescence at 985 nm was demonstrated, proving the great potential of this technology.

Strain engineering of nanowire multi-quantum well demonstrated by Raman spectroscopy.

An analysis of the strain in an axial nanowire superlattice shows that the dominating strain state can be defined arbitrarily between unstrained and maximum mismatch strain by choosing the segment height ratios. We give experimental evidence for a successful strain design in series of GaN nanowire ensembles with axial InxGa1-xN quantum wells. We vary the barrier thickness and determine the strain state of the quantum wells by Raman spectroscopy. A detailed calculation of the strain distribution and LO phonon frequency shift shows that a uniform in-plane lattice constant in the nanowire segments satisfactorily describes the resonant Raman spectra, although in reality the three-dimensional strain profile at the periphery of the quantum wells is complex. Our strain analysis is applicable beyond the InxGa1-xN/GaN system under study, and we derive universal rules for strain engineering in nanowire heterostructures.

Control over the number density and diameter of GaAs nanowires on Si(111) mediated by droplet epitaxy.

We present a novel approach for the growth of GaAs nanowires (NWs) with controllable number density and diameter, which consists of the combination between droplet epitaxy (DE) and self-assisted NW growth. In our method, GaAs islands are initially formed on Si(111) by DE and, subsequently, GaAs NWs are selectively grown on their top facet, which acts as a nucleation site. By DE, we can successfully tailor the number density and diameter of the template of initial GaAs islands and the same degree of control is transferred to the final GaAs NWs. We show how, by a suitable choice of V/III flux ratio, a single NW can be accommodated on top of each GaAs base island. By transmission electron microscopy, as well as cathodo- and photoluminescence spectroscopy, we confirmed the high structural and optical quality of GaAs NWs grown by our method. We believe that this combined approach can be more generally applied to the fabrication of different homo- or heteroepitaxial NWs, nucleated on the top of predefined islands obtained by DE.

GaAs-Fe3Si core-shell nanowires: nanobar magnets.

Semiconductor-ferromagnet GaAs-Fe3Si core-shell nanowires were grown by molecular beam epitaxy and analyzed by scanning and transmission electron microscopy, X-ray diffraction, Mössbauer spectroscopy, and magnetic force microscopy. We obtained closed and smooth Fe3Si shells with a crystalline structure that show ferromagnetic properties with magnetizations along the nanowire axis (perpendicular to the substrate). Such nanobar magnets are promising candidates to enable the fabrication of new forward-looking devices in the field of spintronics and magnetic recording.

Photoelectrochemical properties of (In,Ga)N nanowires for water splitting investigated by in situ electrochemical mass spectroscopy.

We investigated the photoelectrochemical properties of both n- and p-type (In,Ga)N nanowires (NWs) for water splitting by in situ electrochemical mass spectroscopy (EMS). All NWs were prepared by plasma-assisted molecular beam epitaxy. Under illumination, the n-(In,Ga)N NWs exhibited an anodic photocurrent, however, no O2 but only N2 evolution was detected by EMS, indicating that the photocurrent was related to photocorrosion rather than water oxidation. In contrast, the p-(In,Ga)N NWs showed a cathodic photocurrent under illumination which was correlated with the evolution of H2. After photodeposition of Pt on such NWs, the photocurrent density was significantly enhanced to 5 mA/cm(2) at a potential of -0.5 V/NHE under visible light irradiation of ∼40 mW/cm(2). Also, incident photon-to-current conversion efficiencies of around 40% were obtained at -0.45 V/NHE across the entire visible spectral region. The stability of the NW photocathodes for at least 60 min was verified by EMS. These results suggest that p-(In,Ga)N NWs are a promising basis for solar hydrogen production.

Suitability of Au- and self-assisted GaAs nanowires for optoelectronic applications.

The incorporation of Au during vapor-liquid-solid nanowire growth might inherently limit the performance of nanowire-based devices. Here, we assess the material quality of Au-assisted and Au-free grown GaAs/(Al,Ga)As core-shell nanowires using photoluminescence spectroscopy. We show that at room temperature, the internal quantum efficiency is systematically much lower for the Au-assisted nanowires than for the Au-free ones. In contrast, the optoelectronic material quality of the latter is comparable to that of state-of-the-art planar double heterostructures.

Direct probing of Schottky barriers in Si nanowire Schottky barrier field effect transistors.

This work elucidates the role of the Schottky junction in the electronic transport of nanometer-scale transistors. In the example of Schottky barrier silicon nanowire field effect transistors, an electrical scanning probe technique is applied to examine the charge transport effects of a nanometer-scale local top gate during operation. The results prove experimentally that Schottky barriers control the charge carrier transport in these devices. In addition, a proof of concept for a reprogrammable nonvolatile memory device based on band bending at the Schottky barriers will be shown.

Collector phase transitions during vapor-solid-solid nucleation of GaN nanowires.

We investigate the nucleation of Ni-induced GaN nanowires by in situ and ex situ experiments. Three nucleation stages are evidenced. In the first two stages, different crystal structures of the Ni collectors are identified. Real-time monitoring of the Ga desorption allows the amount of Ga incorporated in the collectors to be quantified. A transition of their crystal structure prior to nanowire growth is found to be in agreement with the thermodynamically stable phase sequence of the relevant phase diagrams.

Electroluminescence and current-voltage measurements of single-(In,Ga)N/GaN-nanowire light-emitting diodes in a nanowire ensemble.

We present the combined analysis of electroluminescence (EL) and current-voltage (I-V) behavior of single, freestanding (In,Ga)N/GaN nanowire (NW) light-emitting diodes (LEDs) in an unprocessed, self-assembled ensemble grown by molecular beam epitaxy. The data were acquired in a scanning electron microscope equipped with a micromanipulator and a luminescence detection system. Single NW spectra consist of emission lines originating from different quantum wells, and the width of the spectra increases with decreasing peak emission energy. The corresponding I-V characteristics are described well by a modified Shockley equation. The key advantage of this measurement approach is the possibility to correlate the EL intensity of a single-NW LED with the actual current density in this NW. This way, the external quantum efficiency (EQE) can be investigated as a function of the current in a single-NW LED. The comparison of the EQE characteristic of single NWs and the ensemble device allows for a quite accurate determination of the actual number of emitting NWs in the working ensemble LED and the respective current densities in its individual NWs. This information is decisive for a meaningful and comprehensive characterization of a NW ensemble device, rendering the measurement approach employed here a very powerful analysis tool.

A hybrid MBE-based growth method for large-area synthesis of stacked hexagonal boron nitride/graphene heterostructures.

Van der Waals heterostructures combining hexagonal boron nitride (h-BN) and graphene offer many potential advantages, but remain difficult to produce as continuous films over large areas. In particular, the growth of h-BN on graphene has proven to be challenging due to the inertness of the graphene surface. Here we exploit a scalable molecular beam epitaxy based method to allow both the h-BN and graphene to form in a stacked heterostructure in the favorable growth environment provided by a Ni(111) substrate. This involves first saturating a Ni film on MgO(111) with C, growing h-BN on the exposed metal surface, and precipitating the C back to the h-BN/Ni interface to form graphene. The resulting laterally continuous heterostructure is composed of a top layer of few-layer thick h-BN on an intermediate few-layer thick graphene, lying on top of Ni/MgO(111). Examinations by synchrotron-based grazing incidence diffraction, X-ray photoemission spectroscopy, and UV-Raman spectroscopy reveal that while the h-BN is relaxed, the lattice constant of graphene is significantly reduced, likely due to nitrogen doping. These results illustrate a different pathway for the production of h-BN/graphene heterostructures, and open a new perspective for the large-area preparation of heterosystems combining graphene and other 2D or 3D materials.

Broad Band Light Absorption and High Photocurrent of (In,Ga)N Nanowire Photoanodes Resulting from a Radial Stark Effect.

The photoelectrochemical properties of (In,Ga)N nanowire photoanodes are investigated using H2O2 as a hole scavenger to prevent photocorrosion. Under simulated solar illumination, In0.16Ga0.84N nanowires grown by plasma-assisted molecular beam epitaxy show a high photocurrent of 2.7 mA/cm2 at 1.2 V vs reversible hydrogen electrode. This value is almost the theoretical maximum expected from the corresponding band gap (2.8 eV) for homogeneous bulk material without taking into account surface effects. These nanowires exhibit a higher incident photon-to-current conversion efficiency over a broader wavelength range and a higher photocurrent than a compact layer with higher In content of 28%. These results are explained by the combination of built-in electric fields at the nanowire sidewall surfaces and compositional fluctuations in (In,Ga)N, which gives rise to a radial Stark effect. This effect enables spatially indirect transitions at energies much lower than the band gap. The resulting broad band light absorption leads to high photocurrents. This benefit of the radial Stark effect in (In,Ga)N nanowires for solar harvesting applications opens up the perspective to break the theoretical limit for photocurrents.

Metal-Insulator Transition Driven by Vacancy Ordering in GeSbTe Phase Change Materials.

Phase Change Materials (PCMs) are unique compounds employed in non-volatile random access memory thanks to the rapid and reversible transformation between the amorphous and crystalline state that display large differences in electrical and optical properties. In addition to the amorphous-to-crystalline transition, experimental results on polycrystalline GeSbTe alloys (GST) films evidenced a Metal-Insulator Transition (MIT) attributed to disorder in the crystalline phase. Here we report on a fundamental advance in the fabrication of GST with out-of-plane stacking of ordered vacancy layers by means of three distinct methods: Molecular Beam Epitaxy, thermal annealing and application of femtosecond laser pulses. We assess the degree of vacancy ordering and explicitly correlate it with the MIT. We further tune the ordering in a controlled fashion attaining a large range of resistivity. Employing ordered GST might allow the realization of cells with larger programming windows.

Sub-nanometre resolution of atomic motion during electronic excitation in phase-change materials.

Phase-change materials based on Ge-Sb-Te alloys are widely used in industrial applications such as nonvolatile memories, but reaction pathways for crystalline-to-amorphous phase-change on picosecond timescales remain unknown. Femtosecond laser excitation and an ultrashort x-ray probe is used to show the temporal separation of electronic and thermal effects in a long-lived (>100 ps) transient metastable state of Ge2Sb2Te5 with muted interatomic interaction induced by a weakening of resonant bonding. Due to a specific electronic state, the lattice undergoes a reversible nondestructive modification over a nanoscale region, remaining cold for 4 ps. An independent time-resolved x-ray absorption fine structure experiment confirms the existence of an intermediate state with disordered bonds. This newly unveiled effect allows the utilization of non-thermal ultra-fast pathways enabling artificial manipulation of the switching process, ultimately leading to a redefined speed limit, and improved energy efficiency and reliability of phase-change memory technologies.

Coincident-site lattice matching during van der Waals epitaxy.

Van der Waals (vdW) epitaxy is an attractive method for the fabrication of vdW heterostructures. Here Sb2Te3 films grown on three different kind of graphene substrates (monolayer epitaxial graphene, quasi freestanding bilayer graphene and the SiC (6√3 × 6√3)R30° buffer layer) are used to study the vdW epitaxy between two 2-dimensionally (2D) bonded materials. It is shown that the Sb2Te3 /graphene interface is stable and that coincidence lattices are formed between the epilayers and substrate that depend on the size of the surface unit cell. This demonstrates that there is a significant, although relatively weak, interfacial interaction between the two materials. Lattice matching is thus relevant for vdW epitaxy with two 2D bonded materials and a fundamental design parameter for vdW heterostructures.

Synthesis of quasi-free-standing bilayer graphene nanoribbons on SiC surfaces.

Scaling graphene down to nanoribbons is a promising route for the implementation of this material into devices. Quantum confinement of charge carriers in such nanostructures, combined with the electric field-induced break of symmetry in AB-stacked bilayer graphene, leads to a band gap wider than that obtained solely by this symmetry breaking. Consequently, the possibility of fabricating AB-stacked bilayer graphene nanoribbons with high precision is very attractive for the purposes of applied and basic science. Here we show a method, which includes a straightforward air annealing, for the preparation of quasi-free-standing AB-bilayer nanoribbons with different widths on SiC(0001). Furthermore, the experiments reveal that the degree of disorder at the edges increases with the width, indicating that the narrower nanoribbons are more ordered in their edge termination. In general, the reported approach is a viable route towards the large-scale fabrication of bilayer graphene nanostructures with tailored dimensions and properties for specific applications.